Processing Paper Feedstocks

ABSTRACT

Methods of processing paper feedstocks are provided, as well as intermediates and products made using such methods. Certain types of paper feedstocks, in particular highly pigmented papers, and/or highly loaded papers such as paper that has been color printed, e.g., magazines, and high basis weight coated papers, e.g., magazine stock, are utilized to produce useful intermediates and products, such as energy, fuels, foods or materials.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 61/442,710, filed Feb. 14, 2011. The complete disclosure of thisprovisional application is hereby incorporated by reference herein.

BACKGROUND

Magazines, catalogs, and other paper products that contain high levelsof coatings, pigments, and inks, are widely available as wastematerials. While efforts are made to recycle this waste paper, generallyby repulping it for use in recycled paper products, it would beadvantageous if this waste paper could be economically utilized as afeedstock to make other types of products.

SUMMARY

Generally, this invention relates to methods of processing paperfeedstocks, and to intermediates and products made therefrom. Inparticular, the invention relates generally to the processing of certaintypes of relatively heavy paper feedstocks, such as highly pigmentedpapers, and or loaded papers, such as paper that has been color printed(printed with colors other than or in addition to black), e.g.,magazines, and other papers.

Many of the methods disclosed herein utilize microorganisms or productsproduced by microorganisms, e.g., enzymes, to bioprocess the feedstock,producing useful intermediates and products, e.g., energy, fuels, foodsand other materials. For example, in some cases enzymes are used tosaccharify the feedstocks, converting the feedstocks to sugars. Thesugars may be used as an end product or intermediate, or processedfurther, e.g., by fermentation. For example xylose can be hydrogenatedto xylitol and glucose can be hydrogenated to sorbitol.

In one aspect, the invention features methods for producing a sugar,e.g., in the form of a solution or suspension, that includes providing apaper feedstock, the paper feedstock including offset printing papere.g., offset printed paper, colored paper and/or coated paper e.g.,polycoated paper and optionally mixing the feedstock with a fluid and/orsaccharifying agent.

Some implementations include one or more of the following features. Thepaper feedstock may have a basis weight greater than 35 lb, e.g., fromabout 35 lb to 330 lb and/or the paper may have a high filler content,e.g., greater than about 10 wt. % e.g., greater than 20 wt. %. Forexample, the filler or any coating can be an inorganic material. Thepaper may also have a high grammage, e.g., greater than about 500 g/m².The paper may comprise a pigment or printing ink, e.g., at a levelgreater than about 0.025 wt. %. The paper can have an ash contentgreater than about 8 wt. %.

The method can further include adding a microorganism, for example ayeast and/or a bacteria (e.g., from the genus Clostridium), to the paperfeedstock or saccharified paper and producing a product or intermediate.

The product can be a fuel, including, for example, alcohols (e.g.,methanol, ethanol, propanol, isopropanol, erythritol, n-butanol,isobutanol, sec-butanol, tert-butanol, ethylene glycol, propyleneglycol, 1,4-butane diol and/or glycerin), sugar alcohols (e.g.,erythritol, glycol, glycerol, sorbitol threitol, arabitol, ribitol,mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, lactitol,xylitol and other polyols), organic acids (e.g., formic acid, aceticacid, propionic acid, butyric acid, valeric acid, caproic acid, palmiticacid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaricacid, oleic acid, linoleic acid, glycolic acid, lactic acid and/orγ-hydroxybutyric acid), hydrocarbons (methane, ethane, propane,isobutene, pentane, n-hexane, biodiesels and/or bio-gasolines), hydrogenand mixtures of these.

The method can further include adding a food-based nutrient source tothe mixture, e.g., a nutrient source selected from the group consistingof grains, vegetables, residues of grains, residues of vegetables, andmixtures thereof, for example wheat, oats, barley, soybeans, peas,legumes, potatoes, corn, rice bran, corn meal, wheat bran, and mixturesthereof. In such cases, the mixture can further include an enzyme systemselected to release nutrients from the food-based nutrient source, e.g.,a system comprising a protease and an amylase.

The method can include detoxifying the sugar solution or suspension. Themethod can include further processing the sugar, for example, byseparating xylose and or glucose from the sugar. In some cases, thesaccharification can be conducted at a pH of about 3.8 to 4.2. Themixture can further include a nitrogen source.

In some cases, the method further includes physically treating the paperfeedstock, for example mechanically treating to reduce the bulk densityof the paper feedstock and/or increase the BET surface area of thefeedstock. Physically treating the paper feedstock can includeirradiation, for example, with an electron beam. The method can includemixing the paper feedstock with a fluid. The method can includedetoxifying the paper feedstock, sugar, and/or other products orintermediates. The paper feedstock may be in the form of magazines. Thepaper feedstock may also be a laminate of at least one layer of apolymer and paper and may further include at least one layer of a metale.g., aluminum.

Although many embodiments include the use of relatively heavy paperfeedstocks, e.g., containing fillers and/or coatings other papers can beused e.g., newsprint.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of the present invention, suitable methods andmaterials are described below. All publications, patent applications,patents, and other references mentioned herein are incorporated byreference in their entirety. In case of conflict, the presentspecification, including definitions, will control. In addition, thematerials, methods, and examples are illustrative only and not intendedto be limiting.

Other features and advantages of the invention will be apparent from thefollowing detailed description, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1 is a flow diagram illustrating conversion of a feedstock toethanol via production of a glucose solution.

FIG. 2 is a schematic diagram of an ethanol manufacturing facility.

FIG. 3 is a diagram illustrating the enzymatic hydrolysis of celluloseto glucose.

DETAILED DESCRIPTION

Using the methods and nutrient packages described herein, paperfeedstocks that include high levels of pigments, colors, fillers and/orcoatings, and/or that have a high basis weight, and the saccharifiedderivatives of such feedstocks, can be bioprocessed, e.g., usingfermentation, to produce useful intermediates and products such as thosedescribed herein. In some cases, the feedstock includes high levelspigments and/or fillers such as those feedstocks used in printing, e.g.,magazines. Examples of such feedstocks are described herein. Feedstocksof this type are advantageous for a number of reasons, including theirrelatively low cost (if waste materials are used) and, in the case ofhigh basis weight papers, their relatively high density, whichcontributes to ease of handling and processing.

Converting Cellulosic and Lignocellulosic Materials to Alcohols

Referring to FIG. 1, a process for manufacturing an alcohol, e.g.,ethanol, or a butanol e.g., isobutanol, sec-butanol, tert-butanol orn-butanol, can include, for example, optionally mechanically treatingthe feedstock (step 110), before and/or after this treatment, optionallytreating the feedstock with another physical treatment, for exampleirradiation, to further reduce its recalcitrance (step 112),saccharifying the feedstock to form a sugar solution (step 114),optionally transporting, e.g., by pipeline, railcar, truck or barge, thesolution (or the feedstock, enzyme and water, if saccharification isperformed en route) to a manufacturing plant (step 116), and thenbio-processing the treated feedstock to produce a desired product (step118), which is then processed further, e.g., by distillation (step 120).If desired, lignin content can be measured (step 122) and processparameters can be set or adjusted based on this measurement (step 124),as described in U.S. application Ser. No. 12/704,519, filed on Feb. 11,2010, the complete disclosure of which is incorporated herein byreference.

Because paper feedstocks are generally low in, or entirely lack,nutrients to support bioprocesses, it is generally preferred thatnutrients be added to the system, for example in the form of afood-based nutrient source or nutrient package, as disclosed in U.S.application Ser. No. 13/184,138, incorporated by reference herein in itsentirety. When utilized, the food-based nutrient source or nutrientpackage is present during bio-processing (step 118), e.g., fermentation,and may in some preferred implementations also be present during thesaccharification step (step 114). In some implementations, thefood-based nutrient source or nutrient package is added at the beginningof step 114, along with an enzyme combination suitable forsaccharification, fermentation, and release of nutrients from thefood-based nutrient source.

Saccharification is conducted under a first set of process conditions(e.g., temperature and pH), and then when saccharification has proceededto a desired extent the process conditions may be adjusted (e.g., byadjusting pH from 4 to 5) to allow fermentation to proceed.

In some cases the feedstock includes materials that are not beneficialto the processing of the feedstock or decrease the quality of theintermediates and/or products. For example there may be materials thatare toxic, and/or solid inorganic materials or insoluble organicmaterials. The toxic materials can be detrimental, for example, byreducing the effectiveness of enzymes and/or microorganisms. Examples oftoxic materials are pigments and inks described herein. Solid inorganicmaterials can be detrimental, for example, in increasing the totalviscosity and density of solutions in various processes as well asforming slurries, sludge and settled material that may, for example,block openings, be difficult to remove, e.g., from the bottom of tanks,and/or increase the wear on mixers. Examples of inorganic materials arefillers and coatings described herein. Insoluble organic materials can,for example, contaminate the final fuel products and/or cause foamingduring mixing or other processing steps. Examples of insoluble organicmaterials are polymers used in polycoated paper described herein. It cantherefore be advantageous to remove some of the insoluble solids andorganic materials and to detoxify the feedstock at any point during theprocessing as described herein. Surprisingly, it has been found that insome cases materials in the feedstock that would be expected to bedetrimental, as discussed above, do not significantly adversely affectthe process. For example, some yeasts that provide ethanol byfermentation of sugars derived from paper feedstocks appear to be veryresilient to various pigments, inks and fillers.

The manufacturing plant used in steps 118-120 (and in some cases all ofthe steps described above) can be, for example, an existing starch-basedor sugar-based ethanol plant or one that has been retrofitted byremoving or decommissioning the equipment upstream from thebio-processing system (which in a typical ethanol plant generallyincludes grain receiving equipment, a hammermill, a slurry mixer,cooking equipment and liquefaction equipment). In some cases, thefeedstock received by the plant can be input directly into thefermentation equipment. A retrofitted plant is shown schematically inFIG. 2 and described below as well as, for example, in U.S. Ser. No.12/429,045, filed Apr. 23, 2009, the complete disclosure of which isincorporated herein by reference.

FIG. 2 shows one particular system that utilizes the steps describedabove for treating a feedstock and then using the treated feedstock in afermentation process to produce an alcohol. System 100 includes a module102 in which a feedstock is initially mechanically treated (step 12,above), a module 104 in which the mechanically treated feedstock isstructurally modified (step 14, above), e.g., by irradiation, and amodule 106 in which the structurally modified feedstock is subjected tofurther mechanical treatment (step 16, above). As discussed above, themodule 106 may be of the same type as the module 102, or a differenttype. In some implementations the structurally modified feedstock can bereturned to module 102 for further mechanical treatment rather thanbeing further mechanically treated in a separate module 106.

As described herein, many variations of system 100 can be utilized.

After these treatments, which may be repeated as many times as requiredto obtain desired feedstock properties, the treated feedstock isdelivered to a fermentation system 108. Mixing may be performed duringfermentation, in which case the mixing is preferably relatively gentle(low shear) so as to minimize damage to shear sensitive ingredients suchas enzymes and other microorganisms. In some embodiments, jet mixing isused, as described in U.S. Ser. No. 12/782,694, 13/293,977 and13/293,985, the complete disclosures of which are incorporated herein byreference.

Referring again to FIG. 2, fermentation produces a crude ethanolmixture, which flows into a holding tank 110. Water or other solvent,and other non-ethanol components, are stripped from the crude ethanolmixture using a stripping column 112, and the ethanol is then distilledusing a distillation unit 114, e.g., a rectifier. Distillation may be byvacuum distillation. Finally, the ethanol can be dried using a molecularsieve 116 and/or denatured, if necessary, and output to a desiredshipping method.

In some cases, the systems described herein, or components thereof, maybe portable, so that the system can be transported (e.g., by rail,truck, or marine vessel) from one location to another. The method stepsdescribed herein can be performed at one or more locations, and in somecases one or more of the steps can be performed in transit. Such mobileprocessing is described in U.S. Ser. No. 12/374,549 and InternationalApplication No. WO 2008/011598, the full disclosures of which areincorporated herein by reference.

Any or all of the method steps described herein can be performed atambient temperature. If desired, cooling and/or heating may be employedduring certain steps. For example, the feedstock may be cooled duringmechanical treatment to increase its brittleness. In some embodiments,cooling is employed before, during or after the initial mechanicaltreatment and/or the subsequent mechanical treatment. Cooling may beperformed as described in U.S. Ser. No. 12/502,629, now U.S. Pat. No.7,900,857 the full disclosure of which is incorporated herein byreference. Moreover, the temperature in the fermentation system 108 maybe controlled to enhance saccharification and/or fermentation.

The individual steps of the methods described above, as well as thematerials used, will now be described in further detail.

Physical Treatment

Physical treatment processes can include one or more of any of thosedescribed herein, such as mechanical treatment, chemical treatment,irradiation, sonication, oxidation, pyrolysis or steam explosion.Treatment methods can be used in combinations of two, three, four, oreven all of these technologies (in any order). When more than onetreatment method is used, the methods can be applied at the same time orat different times. Other processes that change a molecular structure ofa feedstock may also be used, alone or in combination with the processesdisclosed herein.

Mechanical Treatments

In some cases, methods can include mechanically treating the feedstock.Mechanical treatments include, for example, cutting, milling, pressing,grinding, shearing and chopping. Milling may include, for example, ballmilling, hammer milling, rotor/stator dry or wet milling, freezermilling, blade milling, knife milling, disk milling, roller milling orother types of milling. Other mechanical treatments include, e.g., stonegrinding, cracking, mechanical ripping or tearing, pin grinding or airattrition milling.

Mechanical treatment can be advantageous for “opening up,” “stressing,”breaking and shattering cellulosic or other materials in the feedstock,making the cellulose of the materials more susceptible to chain scissionand/or reduction of crystallinity. The open materials can also be moresusceptible to oxidation when irradiated.

In some cases, the mechanical treatment may include an initialpreparation of the feedstock as received, e.g., size reduction ofmaterials, such as by cutting, grinding, shearing, pulverizing orchopping. For example, in some cases, loose feedstock (e.g., MachineOffset Paper and/or Polycoated Paper) is prepared by shearing orshredding.

Alternatively, or in addition, the feedstock material can first bephysically treated by one or more of the other physical treatmentmethods, e.g., chemical treatment, radiation, sonication, oxidation,pyrolysis or steam explosion, and then mechanically treated. Thissequence can be advantageous since materials treated by one or more ofthe other treatments, e.g., irradiation or pyrolysis, tend to be morebrittle and, therefore, it may be easier to further change the molecularstructure of the material by mechanical treatment.

In some embodiments, mechanical treatment includes shearing to exposefibers of the material. Shearing can be performed, for example, using arotary knife cutter. Other methods of mechanically treating thefeedstock include, for example, milling or grinding. Milling may beperformed using, for example, a hammer mill, ball mill, colloid mill,conical or cone mill, disk mill, edge mill, Wiley mill or grist mill.Grinding may be performed using, for example, a stone grinder, pingrinder, coffee grinder, or burr grinder. Grinding may be provided, forexample, by a reciprocating pin or other element, as is the case in apin mill. Other mechanical treatment methods include mechanical rippingor tearing, other methods that apply pressure to the material, and airattrition milling. Suitable mechanical treatments further include anyother technique that changes the molecular structure of the feedstock.

If desired, the mechanically treated material can be passed through ascreen, e.g., having an average opening size of 1.59 mm or less ( 1/16inch, 0.0625 inch). In some embodiments, shearing, or other mechanicaltreatment, and screening are performed concurrently. For example, arotary knife cutter can be used to concurrently shear and screen thefeedstock. The feedstock is sheared between stationary blades androtating blades to provide a sheared material that passes through ascreen, and is captured in a bin.

The paper feedstock can be mechanically treated in a dry state (e.g.,having little or no free water on its surface), a hydrated state (e.g.,having up to ten percent by weight absorbed water), or in a wet state,e.g., having between about 10 percent and about 75 percent by weightwater. The fiber source can even be mechanically treated while partiallyor fully submerged under a liquid, such as water, ethanol orisopropanol.

The feedstock can also be mechanically treated under a gas (such as astream or atmosphere of gas other than air), e.g., oxygen or nitrogen,or steam.

Mechanical treatment systems can be configured to produce streams withspecific morphology characteristics such as, for example, surface area,porosity, bulk density, and length-to-width ratio.

In some embodiments, a BET surface area of the mechanically treatedmaterial is greater than 0.1 m²/g, e.g., greater than 0.25 m²/g, greaterthan 0.5 m²/g, greater than 1.0 m²/g, greater than 1.5 m²/g, greaterthan 1.75 m²/g, greater than 5.0 m²/g, greater than 10 m²/g, greaterthan 25 m²/g, greater than 35 m²/g, greater than 50 m²/g, greater than60 m²/g, greater than 75 m²/g, greater than 100 m²/g, greater than 150m²/g, greater than 200 m²/g, or even greater than 250 m²/g.

In some situations, it can be desirable to prepare a low bulk densitymaterial, densify the material (e.g., to make it easier and less costlyto transport to another site), and then revert the material to a lowerbulk density state. Densified materials can be processed by any of themethods described herein, or any material processed by any of themethods described herein can be subsequently densified, e.g., asdisclosed in U.S. Ser. No. 12/429,045 now U.S. Pat. No. 7,932,065 and WO2008/073186, the full disclosures of which are incorporated herein byreference.

Radiation Treatment

One or more radiation processing sequences can be used to process thepaper feedstock, and to provide a structurally modified material whichfunctions as input to further processing steps and/or sequences.Irradiation can, for example, reduce the molecular weight and/orcrystallinity of feedstock. Radiation can also sterilize the materials,or any media needed to bioprocess the material.

In some embodiments, the radiation may be provided by (1) heavy chargedparticles, such as alpha particles or protons, (2) electrons, produced,for example, in beta decay or electron beam accelerators, or (3)electromagnetic radiation, for example, gamma rays, x rays, orultraviolet rays. In one approach, radiation produced by radioactivesubstances can be used to irradiate the feedstock. In another approach,electromagnetic radiation (e.g., produced using electron beam emitters)can be used to irradiate the feedstock. In some embodiments, anycombination in any order or concurrently of (1) through (3) may beutilized. The doses applied depend on the desired effect and theparticular feedstock.

In some instances when chain scission is desirable and/or polymer chainfunctionalization is desirable, particles heavier than electrons, suchas protons, helium nuclei, argon ions, silicon ions, neon ions, carbonions, phosphorus ions, oxygen ions or nitrogen ions can be utilized.When ring-opening chain scission is desired, positively chargedparticles can be utilized for their Lewis acid properties for enhancedring-opening chain scission. For example, when maximum oxidation isdesired, oxygen ions can be utilized, and when maximum nitration isdesired, nitrogen ions can be utilized. The use of heavy particles andpositively charged particles is described in U.S. Ser. No. 12/417,699,now U.S. Pat. No. 7,931,784, the full disclosure of which isincorporated herein by reference.

In one method, a first material that is or includes cellulose having afirst number average molecular weight (M_(N1)) is irradiated, e.g., bytreatment with ionizing radiation (e.g., in the form of gamma radiation,X-ray radiation, 100 nm to 280 nm ultraviolet (UV) light, a beam ofelectrons or other charged particles) to provide a second material thatincludes cellulose having a second number average molecular weight(M_(N2)) lower than the first number average molecular weight. Thesecond material (or the first and second material) can be combined witha microorganism (with or without enzyme treatment) that can utilize thesecond and/or first material or its constituent sugars or lignin toproduce an intermediate or product, such as those described herein.

Since the second material includes cellulose having a reduced molecularweight relative to the first material, and in some instances, a reducedcrystallinity as well, the second material is generally moredispersible, swellable and/or soluble, e.g., in a solution containing amicroorganism and/or an enzyme. These properties make the secondmaterial easier to process and more susceptible to chemical, enzymaticand/or biological attack relative to the first material, which cangreatly improve the production rate and/or production level of a desiredproduct, e.g., ethanol.

In some embodiments, the second number average molecular weight (M_(N2))is lower than the first number average molecular weight (MO by more thanabout 10 percent, e.g., more than about 15, 20, 25, 30, 35, 40, 50percent, 60 percent, or even more than about 75 percent.

In some instances, the second material includes cellulose that has acrystallinity (C₂) that is lower than the crystallinity (C₁) of thecellulose of the first material. For example, (C₂) can be lower than(C₁) by more than about 10 percent, e.g., more than about 15, 20, 25,30, 35, 40, or even more than about 50 percent.

In some embodiments, the second material can have a level of oxidation(O₂) that is higher than the level of oxidation (O₁) of the firstmaterial. A higher level of oxidation of the material can aid in itsdispersability, swellability and/or solubility, further enhancing thematerial's susceptibility to chemical, enzymatic or biological attack.In some embodiments, to increase the level of the oxidation of thesecond material relative to the first material, the irradiation isperformed under an oxidizing environment, e.g., under a blanket of airor oxygen, producing a second material that is more oxidized than thefirst material. For example, the second material can have more hydroxylgroups, aldehyde groups, ketone groups, ester groups or carboxylic acidgroups, which can increase its hydrophilicity.

Ionizing Radiation

Each form of radiation ionizes the paper feedstock via particularinteractions, as determined by the energy of the radiation. Heavycharged particles primarily ionize matter via Coulomb scattering;furthermore, these interactions produce energetic electrons that mayfurther ionize matter. Alpha particles are identical to the nucleus of ahelium atom and are produced by the alpha decay of various radioactivenuclei, such as isotopes of bismuth, polonium, astatine, radon,francium, radium, several actinides, such as actinium, thorium, uranium,neptunium, curium, californium, americium, and plutonium.

When particles are utilized, they can be neutral (uncharged), positivelycharged or negatively charged. When charged, the charged particles canbear a single positive or negative charge, or multiple charges, e.g.,one, two, three or even four or more charges. In instances in whichchain scission is desired, positively charged particles may bedesirable, in part due to their acidic nature. When particles areutilized, the particles can have the mass of a resting electron, orgreater, e.g., 500, 1000, 1500, 2000, 10,000 or even 100,000 times themass of a resting electron. For example, the particles can have a massof from about 1 atomic unit to about 150 atomic units, e.g., from about1 atomic unit to about 50 atomic units, or from about 1 to about 25,e.g., 1, 2, 3, 4, 5, 10, 12 or 15 amu. Accelerators used to acceleratethe particles can be electrostatic DC, electrodynamic DC, RF linear,magnetic induction linear or continuous wave. For example, cyclotrontype accelerators are available from IBA, Belgium, such as theRhodotron® system, while DC type accelerators are available from RDI,now IBA Industrial, such as the Dynamitron®. Ions and ion acceleratorsare discussed in Introductory Nuclear Physics, Kenneth S. Krane, JohnWiley & Sons, Inc. (1988), Krsto Prelec, FIZIKA B 6 (1997) 4, 177-206,Chu, William T., “Overview of Light-Ion Beam Therapy” Columbus-Ohio,ICRU-IAEA Meeting, 18-20 Mar. 2006, Iwata, Y. et al.,“Alternating-Phase-Focused IH-DTL for Heavy-Ion Medical Accelerators”Proceedings of EPAC 2006, Edinburgh, Scotland and Leaner, C. M. et al.,“Status of the Superconducting ECR Ion Source Venus” Proceedings of EPAC2000, Vienna, Austria.

Gamma radiation has the advantage of a significant penetration depthinto a variety of materials. Sources of gamma rays include radioactivenuclei, such as isotopes of cobalt, calcium, technicium, chromium,gallium, indium, iodine, iron, krypton, samarium, selenium, sodium,thalium, and xenon.

Sources of x rays include electron beam collision with metal targets,such as tungsten or molybdenum or alloys, or compact light sources, suchas those produced commercially by Lyncean.

Sources for ultraviolet radiation include deuterium or cadmium lamps.

Sources for infrared radiation include sapphire, zinc, or selenidewindow ceramic lamps.

Sources for microwaves include klystrons, Slevin type RF sources, oratom beam sources that employ hydrogen, oxygen, or nitrogen gases.

In some embodiments, a beam of electrons is used as the radiationsource. A beam of electrons has the advantages of high dose rates (e.g.,1, 5, or even 10 Mrad per second), high throughput, less containment,and less confinement equipment. Electrons can also be more efficient atcausing chain scission. In addition, electrons having energies of 4-10MeV can have a penetration depth of 5 to 30 mm or more, such as 40 mm.

Electron beams can be generated, e.g., by electrostatic generators,cascade generators, transformer generators, low energy accelerators witha scanning system, low energy accelerators with a linear cathode, linearaccelerators, and pulsed accelerators. Electrons as an ionizingradiation source can be useful, e.g., for relatively thin sections ofmaterial, e.g., less than 0.5 inch, e.g., less than 0.4 inch, 0.3 inch,0.2 inch, or less than 0.1 inch. In some embodiments, the energy of eachelectron of the electron beam is from about 0.3 MeV to about 2.0 MeV(million electron volts), e.g., from about 0.5 MeV to about 1.5 MeV, orfrom about 0.7 MeV to about 1.25 MeV.

Electron beam irradiation devices may be procured commercially from IonBeam Applications, Louvain-la-Neuve, Belgium or the Titan Corporation,San Diego, Calif. Typical electron energies can be 1 MeV, 2 MeV, 4.5MeV, 7.5 MeV, or 10 MeV. Typical electron beam irradiation device powercan be 1 kW, 5 kW, 10 kW, 20 kW, 50 kW, 100 kW, 250 kW, or 500 kW. Thelevel of depolymerization of the feedstock depends on the electronenergy used and the dose applied, while exposure time depends on thepower and dose. Typical doses may take values of 1 kGy, 5 kGy, 10 kGy,20 kGy, 50 kGy, 100 kGy, or 200 kGy. In a some embodiments energiesbetween 0.25-10 MeV (e.g., 0.5-0.8 MeV, 0.5-5 MeV, 0.8-4 MeV, 0.8-3 MeV,0.8-2 MeV or 0.8-1.5 MeV) can be used. In some embodiment doses between1-100 Mrad (e.g., 2-80 Mrad, 5-50 Mrad, 5-40 Mrad, 5-30 Mrad or 5-20Mrad) can be used. In some preferred embodiments, an energy between0.8-3 MeV (e.g., 0.8-2 MeV or 0.8-1.5 MeV) combined with doses between5-50 Mrad (e.g., 5-40 Mrad, 5-30 Mrad or 5-20 Mrad) can be used.

Ion Particle Beams

Particles heavier than electrons can be utilized to irradiate paperfeedstock materials. For example, protons, helium nuclei, argon ions,silicon ions, neon ions carbon ions, phosphorus ions, oxygen ions ornitrogen ions can be utilized. In some embodiments, particles heavierthan electrons can induce higher amounts of chain scission (relative tolighter particles). In some instances, positively charged particles caninduce higher amounts of chain scission than negatively chargedparticles due to their acidity.

Heavier particle beams can be generated, e.g., using linear acceleratorsor cyclotrons. In some embodiments, the energy of each particle of thebeam is from about 1.0 MeV/atomic unit (MeV/amu) to about 6,000MeV/atomic unit, e.g., from about 3 MeV/atomic unit to about 4,800MeV/atomic unit, or from about 10 MeV/atomic unit to about 1,000MeV/atomic unit.

In certain embodiments, ion beams used to irradiate paper feedstock caninclude more than one type of ion. For example, ion beams can includemixtures of two or more (e.g., three, four or more) different types ofions. Exemplary mixtures can include carbon ions and protons, carbonions and oxygen ions, nitrogen ions and protons, and iron ions andprotons. More generally, mixtures of any of the ions discussed above (orany other ions) can be used to form irradiating ion beams. Inparticular, mixtures of relatively light and relatively heavier ions canbe used in a single ion beam.

In some embodiments, ion beams for irradiating paper feedstock includepositively-charged ions. The positively charged ions can include, forexample, positively charged hydrogen ions (e.g., protons), noble gasions (e.g., helium, neon, argon), carbon ions, nitrogen ions, oxygenions, silicon atoms, phosphorus ions, and metal ions such as sodiumions, calcium ions, and/or iron ions. Without wishing to be bound by anytheory, it is believed that such positively-charged ions behavechemically as Lewis acid moieties when exposed to materials, initiatingand sustaining cationic ring-opening chain scission reactions in anoxidative environment.

In certain embodiments, ion beams for irradiating paper feedstockinclude negatively-charged ions. Negatively charged ions can include,for example, negatively charged hydrogen ions (e.g., hydride ions), andnegatively charged ions of various relatively electronegative nuclei(e.g., oxygen ions, nitrogen ions, carbon ions, silicon ions, andphosphorus ions). Without wishing to be bound by any theory, it isbelieved that such negatively-charged ions behave chemically as Lewisbase moieties when exposed to materials, causing anionic ring-openingchain scission reactions in a reducing environment.

In some embodiments, beams for irradiating paper feedstock can includeneutral atoms. For example, any one or more of hydrogen atoms, heliumatoms, carbon atoms, nitrogen atoms, oxygen atoms, neon atoms, siliconatoms, phosphorus atoms, argon atoms, and iron atoms can be included inbeams that are used for irradiation. In general, mixtures of any two ormore of the above types of atoms (e.g., three or more, four or more, oreven more) can be present in the beams.

In certain embodiments, ion beams used to irradiate paper feedstockinclude singly-charged ions such as one or more of H⁺, H⁻, He⁺, Ne⁺,Ar⁺, C⁺, C⁻, O⁺, O⁻, N⁺, N⁻, Si⁺, Si⁻, P⁺, P⁻, Na⁺, Ca⁺, and Fe⁺. Insome embodiments, ion beams can include multiply-charged ions such asone or more of C²⁺, C³⁺, C⁴⁺, N³⁺, N⁵⁺, N³⁺, O²⁺, O²⁺, O²⁻, O₂ ²⁻, Si²⁺,Si⁴⁺, Si²⁻, and Si⁴⁻. In general, the ion beams can also include morecomplex polynuclear ions that bear multiple positive or negativecharges. In certain embodiments, by virtue of the structure of thepolynuclear ion, the positive or negative charges can be effectivelydistributed over substantially the entire structure of the ions. In someembodiments, the positive or negative charges can be somewhat localizedover portions of the structure of the ions.

Electromagnetic Radiation

In embodiments in which the irradiating is performed withelectromagnetic radiation, the electromagnetic radiation can have, e.g.,energy per photon (in electron volts) of greater than 10² eV, e.g.,greater than 10³, 10⁴, 10⁵, 10⁶, or even greater than 10⁷ eV. In someembodiments, the electromagnetic radiation has energy per photon ofbetween 10⁴ and 10⁷, e.g., between 10⁵ and 10⁶ eV. The electromagneticradiation can have a frequency of, e.g., greater than 10¹⁶ hz, greaterthan 10¹⁷ hz, 10¹⁸, 10¹⁹, 10²⁰, or even greater than 10²¹ hz. Typicaldoses may take values of greater than 1 Mrad (e.g., greater than 1 Mrad,greater than 2 Mrad). In some embodiments, the electromagnetic radiationhas a frequency of between 10¹⁸ and 10²² hz, e.g., between 10¹⁹ to 10²¹hz. In some embodiment doses between 1-100 Mrad (e.g., 2-80 Mrad, 5-50Mrad, 5-40 Mrad, 5-30 Mrad or 5-20 Mrad) can be used.

Quenching and Controlled Functionalization

After treatment with ionizing radiation, any of the materials ormixtures described herein may become ionized; that is, the treatedmaterial may include radicals at levels that are detectable with anelectron spin resonance spectrometer. If an ionized feedstock remains inthe atmosphere, it will be oxidized, such as to an extent thatcarboxylic acid groups are generated by reacting with the atmosphericoxygen. In some instances with some materials, such oxidation is desiredbecause it can aid in the further breakdown in molecular weight of thecarbohydrate-containing biomass, and the oxidation groups, e.g.,carboxylic acid groups can be helpful for solubility and microorganismutilization in some instances. However, since the radicals can “live”for some time after irradiation, e.g., longer than 1 day, 5 days, 30days, 3 months, 6 months or even longer than 1 year, material propertiescan continue to change over time, which in some instances, can beundesirable. Thus, it may be desirable to quench the ionized material.

After ionization, any ionized material can be quenched to reduce thelevel of radicals in the ionized material, e.g., such that the radicalsare no longer detectable with the electron spin resonance spectrometer.For example, the radicals can be quenched by the application of asufficient pressure to the material and/or by utilizing a fluid incontact with the ionized material, such as a gas or liquid, that reactswith (quenches) the radicals. Using a gas or liquid to at least aid inthe quenching of the radicals can be used to functionalize the ionizedmaterial with a desired amount and kind of functional groups, such ascarboxylic acid groups, enol groups, aldehyde groups, nitro groups,nitrile groups, amino groups, alkyl amino groups, alkyl groups,chloroalkyl groups or chlorofluoroalkyl groups.

In some instances, such quenching can improve the stability of some ofthe ionized materials. For example, quenching can improve the resistanceof the material to oxidation. Functionalization by quenching can alsoimprove the solubility of any material described herein, can improve itsthermal stability, and can improve material utilization by variousmicroorganisms. For example, the functional groups imparted to thematerial by the quenching can act as receptor sites for attachment bymicroorganisms, e.g., to enhance cellulose hydrolysis by variousmicroorganisms.

In some embodiments, quenching includes an application of pressure tothe ionized material, such as by mechanically deforming the material,e.g., directly mechanically compressing the material in one, two, orthree dimensions, or applying pressure to a fluid in which the materialis immersed, e.g., isostatic pressing. In such instances, thedeformation of the material itself brings radicals, which are oftentrapped in crystalline domains, in close enough proximity so that theradicals can recombine, or react with another group. In some instances,the pressure is applied together with the application of heat, such as asufficient quantity of heat to elevate the temperature of the materialto above a melting point or softening point of a component of thematerial, such cellulose or another polymer. Heat can improve molecularmobility in the material, which can aid in the quenching of theradicals. When pressure is utilized to quench, the pressure can begreater than about 1000 psi, such as greater than about 1250 psi, 1450psi, 3625 psi, 5075 psi, 7250 psi, 10000 psi or even greater than 15000psi.

In some embodiments, quenching includes contacting the ionized materialwith a fluid, such as a liquid or gas, e.g., a gas capable of reactingwith the radicals, such as acetylene or a mixture of acetylene innitrogen, ethylene, chlorinated ethylenes or chlorofluoroethylenes,propylene or mixtures of these gases. In other particular embodiments,quenching includes contacting the ionized material with a liquid, e.g.,a liquid soluble in, or at least capable of penetrating into thematerial and reacting with the radicals, such as a diene, such as1,5-cyclooctadiene. In some specific embodiments, quenching includescontacting the material with an antioxidant, such as Vitamin E. Ifdesired, the feedstock can include an antioxidant dispersed therein, andthe quenching can come from contacting the antioxidant dispersed in thefeedstock with the radicals. Functionalization can be enhanced byutilizing heavy charged ions, such as any of the heavier ions describedherein. For example, if it is desired to enhance oxidation, chargedoxygen ions can be utilized for the irradiation. If nitrogen functionalgroups are desired, nitrogen ions or anions that include nitrogen can beutilized. Likewise, if sulfur or phosphorus groups are desired, sulfuror phosphorus ions can be used in the irradiation.

Doses

In some instances, the irradiation is performed at a dosage rate ofgreater than about 0.25 Mrad per second, e.g., greater than about 0.5,0.75, 1.0, 1.5, 2.0, or even greater than about 2.5 Mrad per second. Insome embodiments, the irradiating is performed at a dose rate of between5.0 and 1500.0 kilorads/hour, e.g., between 10.0 and 750.0 kilorads/houror between 50.0 and 350.0 kilorads/hour. In some embodiments,irradiation is performed at a dose rate of greater than about 0.25 Mradper second, e.g., greater than about 0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12,15, or even greater than about 20 Mrad per second, e.g., about 0.25 to 2Mrad per second.

In some embodiments, the irradiating (with any radiation source or acombination of sources) is performed until the material receives a doseof 0.25 Mrad, e.g., at least 1.0, 2.5, 5.0, 8.0, 10, 15, 20, 25, 30, 35,40, 50, or even at least 100 Mrad. In some embodiments, the irradiatingis performed until the material receives a dose of between 1.0 Mrad and6.0 Mrad, e.g., between 1.5 Mrad and 4.0 Mrad, 2 Mrad and 10 Mrad, 5Mrad and 20 Mrad, 10 Mrad and 30 Mrad, 10 Mrad and 40 Mrad, or 20 Mradand 50 Mrad. In some embodiments, the irradiating is performed until thematerial receives a dose of from about 0.1 Mrad to about 500 Mrad, fromabout 0.5 Mrad to about 200 Mrad, from about 1 Mrad to about 100 Mrad,or from about 5 Mrad to about 60 Mrad. In some embodiments, a relativelylow dose of radiation is applied, e.g., less than 60 Mrad.

Sonication

Sonication can reduce the molecular weight and/or crystallinity of thepolymers comprising the paper feedstock, e.g., cellulose. Sonication canalso be used to sterilize the materials. As discussed above with regardto radiation, the process parameters used for sonication can be varieddepending on various factors.

In one method, a first material that includes cellulose having a firstnumber average molecular weight (M_(N1)) is dispersed in a medium, suchas water, and sonicated and/or otherwise cavitated, to provide a secondmaterial that includes cellulose having a second number averagemolecular weight (M_(N2)) lower than the first number average molecularweight. The second material (or the first and second material in certainembodiments) can be combined with a microorganism (with or withoutenzyme treatment) that can utilize the second and/or first material toproduce an intermediate or product.

Since the second material includes cellulose having a reduced molecularweight relative to the first material, and in some instances, a reducedcrystallinity as well, the second material is generally moredispersible, swellable, and/or soluble, e.g., in a solution containing amicroorganism.

In some embodiments, the second number average molecular weight (M_(N2))is lower than the first number average molecular weight (M_(N1)) by morethan about 10 percent, e.g., more than about 15, 20, 25, 30, 35, 40, 50percent, 60 percent, or even more than about 75 percent.

In some instances, the second material includes cellulose that has acrystallinity (C₂) that is lower than the crystallinity (C₁) of thecellulose of the first material. For example, (C₂) can be lower than(C₁) by more than about 10 percent, e.g., more than about 15, 20, 25,30, 35, 40, or even more than about 50 percent.

In some embodiments, the sonication medium is an aqueous medium. Ifdesired, the medium can include an oxidant, such as a peroxide (e.g.,hydrogen peroxide), a dispersing agent and/or a buffer. Examples ofdispersing agents include ionic dispersing agents, e.g., sodium laurylsulfate, and non-ionic dispersing agents, e.g., poly(ethylene glycol).

In other embodiments, the sonication medium is non-aqueous. For example,the sonication can be performed in a hydrocarbon, e.g., toluene orheptane, an ether, e.g., diethyl ether or tetrahydrofuran, or even in aliquefied gas such as argon, xenon, or nitrogen.

Pyrolysis

One or more pyrolysis processing sequences can be used to process paperfeedstock from a wide variety of different sources to extract usefulsubstances from the materials, and to provide partially degradedmaterials which function as input to further processing steps and/orsequences. Pyrolysis can also be used to sterilize the materials.Pyrolysis conditions can be varied depending on the characteristics ofthe feedstock and/or other factors.

In one example, a first material that includes cellulose having a firstnumber average molecular weight (M_(N1)) is pyrolyzed, e.g., by heatingthe first material in a tube furnace (in the presence or absence ofoxygen), to provide a second material that includes cellulose having asecond number average molecular weight (M_(N2)) lower than the firstnumber average molecular weight.

Since the second material includes cellulose having a reduced molecularweight relative to the first material, and in some instances, a reducedcrystallinity as well, the second material is generally moredispersible, swellable and/or soluble, e.g., in a solution containing amicroorganism.

In some embodiments, the second number average molecular weight (M_(N2))is lower than the first number average molecular weight (M_(N1)) by morethan about 10 percent, e.g., more than about 15, 20, 25, 30, 35, 40, 50percent, 60 percent, or even more than about 75 percent.

In some instances, the second material includes cellulose that has acrystallinity (C₂) that is lower than the crystallinity (C₁) of thecellulose of the first material. For example, (C₂) can be lower than(C₁) by more than about 10 percent, e.g., more than about 15, 20, 25,30, 35, 40, or even more than about 50 percent.

In some embodiments, the pyrolysis of the materials is continuous. Inother embodiments, the material is pyrolyzed for a pre-determined time,and then allowed to cool for a second pre-determined time beforepyrolyzing again.

Oxidation

One or more oxidative processing sequences can be used to process paperfeestock from a wide variety of different sources to extract usefulsubstances from the feedstock, and to provide partially degraded and/oraltered feedstock which functions as input to further processing stepsand/or sequences. The oxidation conditions can be varied, e.g.,depending on the lignin content of the feedstock, with a higher degreeof oxidation generally being desired for higher lignin contentfeedstocks.

In one method, a first material that includes cellulose having a firstnumber average molecular weight (MO and having a first oxygen content(O₁) is oxidized, e.g., by heating the first material in a stream of airor oxygen-enriched air, to provide a second material that includescellulose having a second number average molecular weight (M_(N2)) andhaving a second oxygen content (O₂) higher than the first oxygen content(O₁).

The second number average molecular weight of the second material isgenerally lower than the first number average molecular weight of thefirst material. For example, the molecular weight may be reduced to thesame extent as discussed above with respect to the other physicaltreatments. The crystallinity of the second material may also be reducedto the same extent as discussed above with respect to the other physicaltreatments.

In some embodiments, the second oxygen content is at least about fivepercent higher than the first oxygen content, e.g., 7.5 percent higher,10.0 percent higher, 12.5 percent higher, 15.0 percent higher or 17.5percent higher. In some preferred embodiments, the second oxygen contentis at least about 20.0 percent higher than the first oxygen content ofthe first material. Oxygen content is measured by elemental analysis bypyrolyzing a sample in a furnace operating at 1300° C. or higher. Asuitable elemental analyzer is the LECO CHNS-932 analyzer with a VTF-900high temperature pyrolysis furnace.

Generally, oxidation of a material occurs in an oxidizing environment.For example, the oxidation can be effected or aided by pyrolysis in anoxidizing environment, such as in air or argon enriched in air. To aidin the oxidation, various chemical agents, such as oxidants, acids orbases can be added to the material prior to or during oxidation. Forexample, a peroxide (e.g., benzoyl peroxide) can be added prior tooxidation.

Some oxidative methods of reducing recalcitrance in a paper feedstockemploy Fenton-type chemistry. Such methods are disclosed, for example,in U.S. Ser. No. 12/639,289, the complete disclosure of which isincorporated herein by reference.

Exemplary oxidants include peroxides, such as hydrogen peroxide andbenzoyl peroxide, persulfates, such as ammonium persulfate, activatedforms of oxygen, such as ozone, permanganates, such as potassiumpermanganate, perchlorates, such as sodium perchlorate, andhypochlorites, such as sodium hypochlorite (household bleach).

In some situations, pH is maintained at or below about 5.5 duringcontact, such as between 1 and 5, between 2 and 5, between 2.5 and 5 orbetween about 3 and 5. Oxidation conditions can also include a contactperiod of between 2 and 12 hours, e.g., between 4 and 10 hours orbetween 5 and 8 hours. In some instances, temperature is maintained ator below 300° C., e.g., at or below 250, 200, 150, 100 or 50° C. In someinstances, the temperature remains substantially ambient, e.g., at orabout 20-25° C.

In some embodiments, the one or more oxidants are applied as a gas, suchas by generating ozone in-situ by irradiating the material through airwith a beam of particles, such as electrons.

In some embodiments, the mixture further includes one or morehydroquinones, such as 2,5-dimethoxyhydroquinone (DMHQ) and/or one ormore benzoquinones, such as 2,5-dimethoxy-1,4-benzoquinone (DMBQ), whichcan aid in electron transfer reactions.

In some embodiments, the one or more oxidants areelectrochemically-generated in-situ. For example, hydrogen peroxideand/or ozone can be electro-chemically produced within a contact orreaction vessel.

Other Processes to Solubilize, Reduce Recalcitrance or to Functionalize

Any of the processes of this paragraph can be used alone without any ofthe processes described herein, or in combination with any of theprocesses described herein (in any order): steam explosion, chemicaltreatment (e.g., acid treatment (including concentrated and dilute acidtreatment with mineral acids, such as sulfuric acid, hydrochloric acidand organic acids, such as trifluoroacetic acid) and/or base treatment(e.g., treatment with lime or sodium hydroxide)), UV treatment, screwextrusion treatment (see, e.g., U.S. Ser. No. 13/099,151, solventtreatment (e.g., treatment with ionic liquids) and freeze milling (see,e.g., U.S. Ser. No. 12/502,629 now U.S. Pat. No. 7,900,857).

Saccharification

In order to convert the paper feedstock to fermentable sugars, thecellulose in the feedstock is hydrolyzed by a saccharifying agent, e.g.,an enzyme, a process referred to as saccharification. The materials thatinclude the cellulose are treated with the enzyme, e.g., by combiningthe material and the enzyme in a solvent, e.g., in an aqueous solution.

Enzymes and organisms that break down cellulose contain or manufacturevarious cellulolytic enzymes (cellulases), ligninases or various smallmolecule biomass-destroying metabolites. These enzymes may be a complexof enzymes that act synergistically to degrade crystalline cellulose.Examples of cellulolytic enzymes include: endoglucanases,cellobiohydrolases, and cellobiases (β-glucosidases). Referring to FIG.3, a cellulosic substrate is initially hydrolyzed by endoglucanases atrandom locations producing oligomeric intermediates. These intermediatesare then substrates for exo-splitting glucanases such ascellobiohydrolase to produce cellobiose from the ends of the cellulosepolymer. Cellobiose is a water-soluble 1,4-linked dimer of glucose.Finally cellobiase cleaves cellobiose to yield glucose.

Suitable saccharifying agents are described, for example, in theMaterials section below.

As noted above, a food-based nutrient source or nutrient package ispreferably added prior to or during saccharification, and an enzyme isadded that is selected to release nutrients from the food-based nutrientsource. Suitable enzymes are described, for example, in the Materialssection below.

The saccharification process can be partially or completely performed ina tank (e.g., a tank having a volume of at least 4000, 40,000, 400,000 Lor 1,000,000 L) in a manufacturing plant, and/or can be partially orcompletely performed in transit, e.g., in a rail car, tanker truck, orin a supertanker or the hold of a ship. The time required for completesaccharification will depend on the process conditions and the feedstockand enzyme used. If saccharification is performed in a manufacturingplant under controlled conditions, the cellulose may be substantiallyentirely converted to glucose in about 12-96 hours. If saccharificationis performed partially or completely in transit, saccharification maytake longer.

It is generally preferred that the tank contents be mixed duringsaccharification, e.g., using jet mixing as described in U.S.application Ser. Nos. 12/782,694, 13/293,985 and 13/293,977, the fulldisclosure of which are incorporated by reference herein.

The addition of surfactants can enhance the rate of saccharification.Examples of surfactants include non-ionic surfactants, such as a Tween®20 or Tween® 80 polyethylene glycol surfactants, ionic surfactants, oramphoteric surfactants.

It is generally preferred that the concentration of the resultingglucose solution be relatively high, e.g., greater than 40%, or greaterthan 50, 60, 70, 80, 90 or even greater than 95% by weight. This reducesthe volume to be shipped, if saccharification and fermentation areperformed at different locations, and also inhibits microbial growth inthe solution. However, lower concentrations may be used, in which caseit may be desirable to add an antimicrobial additive, e.g., a broadspectrum antibiotic, in a low concentration, e.g., 50 to 150 ppm. Othersuitable antibiotics include amphotericin B, ampicillin,chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin,neomycin, penicillin, puromycin, streptomycin. Antibiotics will inhibitgrowth of microorganisms during transport and storage, and can be usedat appropriate concentrations, e.g., between 15 and 1000 ppm by weight,e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If desired, anantibiotic can be included even if the sugar concentration is relativelyhigh.

A relatively high concentration solution can be obtained by limiting theamount of water added to the feedstock with the enzyme. Theconcentration can be controlled, e.g., by controlling how muchsaccharification takes place. For example, concentration can beincreased by adding more feedstock to the solution. In order to keep thesugar that is being produced in solution, a surfactant can be added,e.g., one of those discussed above. Solubility can also be increased byincreasing the temperature of the solution. For example, the solutioncan be maintained at a temperature of 40-50° C., 60-80° C., or evenhigher.

In some embodiments, the feedstock is processed to convert it to aconvenient and concentrated solid material, e.g., in a powdered,granulate or particulate form. The concentrated material can be in apurified, or a raw or crude form. The concentrated form can have, forexample, a total sugar concentration of between about 90 percent byweight and about 100 percent by weight, e.g., 92, 94, 96 or 98 percentby weight sugar. Such a form can be particularly cost effective to ship,e.g., to a bioprocessing facility, such as a biofuel manufacturingplant. Such a form can also be advantageous to store and handle, easierto manufacture and becomes both an intermediate and a product, providingan option to the biorefinery as to which products to manufacture.

In some instances, the powdered, granulate or particulate material canalso include one or more of the materials, e.g., additives or chemicals,described herein, such as the food-based nutrient or nutrient package, anitrogen source, e.g., urea, a surfactant, an enzyme, or anymicroorganism described herein. In some instances, all materials neededfor a bio-process are combined in the powdered, granulate or particulatematerial. Such a form can be a particularly convenient form fortransporting to a remote bioprocessing facility, such as a remotebiofuels manufacturing facility. Such a form can also be advantageous tostore and handle.

In some instances, the powdered, granulate or particulate material (withor without added materials, such as additives and chemicals) can betreated by any of the physical treatments described in U.S. Ser. No.12/429,045, incorporated by reference above. For example, irradiatingthe powdered, granulate or particulate material can increase itssolubility and can sterilize the material so that a bioprocessingfacility can integrate the material into their process directly as maybe required for a contemplated intermediate or product.

In certain instances, the powdered, granulate or particulate material(with or without added materials, such as additives and chemicals) canbe carried in a structure or a carrier for ease of transport, storage orhandling. For example, the structure or carrier can include orincorporate a bag or liner, such as a degradable bag or liner. Such aform can be particularly useful for adding directly to a bioprocesssystem.

Fermentation

Microorganisms can produce a number of useful intermediates and productsby fermenting a low molecular weight sugar produced by saccharifying thepaper feedstock materials. For example, fermentation or otherbioprocesses can produce alcohols, organic acids, hydrocarbons,hydrogen, proteins or mixtures of any of these materials.

Yeast and Zymomonas bacteria, for example, can be used for fermentationor conversion. Other microorganisms are discussed in the Materialssection, below. The optimum pH for fermentations is about pH 4 to 7. Forexample, the optimum pH for yeast is from about pH 4 to 5, while theoptimum pH for Zymomonas is from about pH 5 to 6. Typical fermentationtimes are about 24 to 168 hours (e.g., 24 to 96 hrs) with temperaturesin the range of 20° C. to 40° C. (e.g., 26° C. to 40° C.), howeverthermophilic microorganisms prefer higher temperatures.

In some embodiments e.g., when anaerobic organisms are used, at least aportion of the fermentation is conducted in the absence of oxygen e.g.,under a blanket of an inert gas such as N₂, Ar, He, CO₂ or mixturesthereof. Additionally, the mixture may have a constant purge of an inertgas flowing through the tank during part of or all of the fermentation.In some cases, anaerobic condition can be achieved or maintained bycarbon dioxide production during the fermentation and no additionalinert gas is needed.

In some embodiments, all or a portion of the fermentation process can beinterrupted before the low molecular weight sugar is completelyconverted to a product (e.g, ethanol). The intermediate fermentationproducts include high concentrations of sugar and carbohydrates. Thesugars and carbohydrates can be isolated as discussed below. Theseintermediate fermentation products can be used in preparation of foodfor human or animal consumption. Additionally or alternatively, theintermediate fermentation products can be ground to a fine particle sizein a stainless-steel laboratory mill to produce a flour-like substance.

The fermentations include the methods and products that are disclosed inU.S. Provisional Application Ser. No. 61/579,559, filed Dec. 22, 2012,and U.S. application 61/579,576, filed Dec. 22, 2012 incorporated byreference herein in its entirety.

Mobile fermentors can be utilized, as described in U.S. ProvisionalPatent Application Ser. 60/832,735, now Published InternationalApplication No. WO 2008/011598. Similarly, the saccharificationequipment can be mobile. Further, saccharification and/or fermentationmay be performed in part or entirely during transit.

Distillation

After fermentation, the resulting fluids can be distilled using, forexample, a “beer column” to separate ethanol and other alcohols from themajority of water and residual solids. The vapor exiting the beer columncan be, e.g., 35% by weight ethanol and can be fed to a rectificationcolumn. A mixture of nearly azeotropic (92.5%) ethanol and water fromthe rectification column can be purified to pure (99.5%) ethanol usingvapor-phase molecular sieves. The beer column bottoms can be sent to thefirst effect of a three-effect evaporator. The rectification columnreflux condenser can provide heat for this first effect. After the firsteffect, solids can be separated using a centrifuge and dried in a rotarydryer. A portion (25%) of the centrifuge effluent can be recycled tofermentation and the rest sent to the second and third evaporatoreffects. Most of the evaporator condensate can be returned to theprocess as fairly clean condensate with a small portion split off towaste water treatment to prevent build-up of low-boiling compounds.

Other Possible Processing of Sugars

Processing during or after saccharification can include isolation and/orconcentration of sugars by chromatography e.g., simulated moving bedchromatography, precipitation, centrifugation, crystallization, solventevaporation and combinations thereof. In addition, or optionally,processing can include isomerization of one or more of the sugars in thesugar solution or suspension. Additionally, or optionally, the sugarsolution or suspension can be chemically processed e.g., glucose andxylose can be hydrogenated to sorbitol and xylitol respectively.Hydrogenation can be accomplished by use of a catalyst e.g., Pt/γ-Al₂O₃,Ru/C, Raney Nickel in combination with H₂ under high pressure e.g., 10to 12000 psi.

Some possible processing steps are disclosed in in U.S. ProvisionalApplication Ser. No. 61/579,552, filed Dec. 22, 2012, and in U.S.Provisional Application Ser. No. 61/579,576 filed Dec. 22, 2012,incorporated by reference herein in its entirety above.

Removing of Fillers, Inks, and Coatings

Paper feedstock used in the processes described can contain fillers,coatings, laminated material, pigments, inks and binders. These can beremoved and either discarded or recycled as described here.

Inorganic fillers and coatings e.g., those described in the materialssection below can be removed at any point during the process. Forexample, the inorganic filler and coating can be removed from thefeedstock after a mechanical, physical or chemical treatment to reducethe recalcitrance of the feedstock; after combination with a fluid;after, during or before saccharification; after, during or before apurification step; after, during or before a fermentation step; and/orafter, during or before a chemical conversion step. The fillers andcoatings can be removed by any means e.g., by sedimentation,precipitation, ligand sequestration, filtration, floatation, chemicalconversion and centrifugation. Some of the physical treatments discussedherein (see Physical Treatment section) can aid in separating thecellulosic materials from the inorganic fillers and coatings (e.g.,mechanical treatments, chemical treatments, irradiation, pyrolysis,sonication and/or oxidation). The recovered inorganic fillers can berecycled or discarded.

Inks that are present can be removed from the feedstock at any pointduring the process. Inks can be a complex medium composed of severalcomponents e.g., solvents, pigments, dyes, resins, lubricants,solubilizers, surfactants, particulate matter and/or fluorescers. Forexample, printed papers, e.g., magazines and catalogs, may include highlevels of the pigments generally used in printing inks. In some casesthe papers include metal-based pigments, organic pigments, and/or Lakepigments. For example, pigments that can be used are Yellow Lakes,Tartrazine Yellow Lake, Hansa Yellows, Diarylide Yellows, Yellow azopigments, Fluorescent Yellow, Diarylide Orange, DNA Orange, PyrazoloneOrange, Fast Orange F2G, Benzimidazolone Orange HL, Ethyl Lake Red C,Para Reds, Toluidine Red, Carmine F.B., Naphthol Reds and Rubines,Permanent Red FRC, Bordeaux FRR, Rubine Reds, Lithol Reds, BON Red,Lithol Rubine 4B, BON Maroon, Rhodamine 6G, Lake Red C, BON ArylamideRed, Quinacrinone Magentas, Copper Ferrocyanide Pink, BenzimidazoloneCarmines and Reds, Azo Magenta G, Anthraquinone Scarlet, Madder Lakes,Phthalocyanine Blues, PMTA Victoria Blue, Victoria Blue CFA, UltramarineBlue, Indanthrene Blue, Alkali Blues, Peacock Blue, BenzimidazoloneBordeaux HF 3R, PMTA Rhodamine, PMTA Violet, Dioxazine Violet, CarbazoleViolet, Crystal Violet, Dioxazine Violet B, Thioindigoid Red,Phthalocyanine Greens, PMTA Greens, Benzimidazolone Brown HFR, CadmiumRed, Cadmium Yellow, Cadmium Oranges, Cadmium-Mercury Reds, Iron OxideYellows, Irons Oxide Blues, Iron Oxide browns, Iron Oxide Reds,Ultramarine Blues, Ultramarine Violet, Chromium Antimony Titanium Buff,copper phthalocyanine blue, green copper phthalocyanine pigments, potashblue and soda blue pigments. The removal of ink may help improve certainparts in the process. For example, some ink can be toxic tomicroorganisms used in the process. The inks can also impart anundesirable coloration or toxicity to the final product. Furthermore,removing the inks may allow these to be recycled, improving the costbenefits to the process and lessening the environmental impact of thepaper feedstock. The inks can be removed by any means. For example,removal may include dispersion, floatation, pressing and/or washingsteps, extraction with solvents (e.g., supercritical CO₂, alcohol, waterand organic solvents), settling, chemical means, sieving and/orprecipitation. Some of the physical treatments discussed herein (seePhysical Treatment section) can aid in separating the cellulosicmaterials from the inks (e.g., mechanical treatments, chemicaltreatments, irradiation, pyrolysis, sonication and/or oxidation). Inaddition enzymatic deinking technologies such as those disclosed in U.S.Pat. No. 7,297,224 hereby incorporated by reference herein, can be used.

Coating materials, e.g., those found in poly-coated paper described inthe materials section below, can be removed from the feedstock at anypoint during the process. This can be done by, for example, the methodsmentioned above for removal of pigments and inks and inorganicmaterials. In some cases, where polycoated paper is a laminate,de-lamination can be done by, for example, chemical and/or mechanicalmeans. The non-cellulosic laminate portions can then be separated fromthe cellulose containing layers and discarded and/or recycled.

Intermediates and Products

The processes and nutrients discussed herein can be used to convertpaper feedstocks to one or more products, such as energy, fuels, foodsand materials. Specific examples of products include, but are notlimited to, hydrogen, sugars (e.g., glucose, xylose, arabinose, mannose,galactose, fructose, disaccharides, oligosaccharides andpolysaccharides), alcohols (e.g., monohydric alcohols or dihydricalcohols, such as ethanol, n-propanol, isobutanol, sec-butanol,tert-butanol or n-butanol), hydrated or hydrous alcohols, e.g.,containing greater than 10%, 20%, 30% or even greater than 40% water,sugars, biodiesel, organic acids (e.g., acetic acid and/or lactic acid),hydrocarbons, e.g., methane, ethane, propane, isobutene, pentane,n-hexane, biodiesel, bio-gasoline and mixtures thereof, co-products(e.g., proteins, such as cellulolytic proteins (enzymes) or single cellproteins), and mixtures of any of these in any combination or relativeconcentration, and optionally in combination with any additives, e.g.,fuel additives. Other examples include carboxylic acids, such as aceticacid or butyric acid, salts of a carboxylic acid, a mixture ofcarboxylic acids and salts of carboxylic acids and esters of carboxylicacids (e.g., methyl, ethyl and n-propyl esters), ketones, aldehydes,alpha, beta unsaturated acids, such as acrylic acid and olefins, such asethylene. Other alcohols and alcohol derivatives include propanol,propylene glycol, 1,4-butanediol, 1,3-propanediol, sugar alcohols (e.g.,erythritol, glycol, glycerol, sorbitol threitol, arabitol, ribitol,mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, lactitol,xylitol and other polyols), methyl or ethyl esters of any of thesealcohols. Other products include methyl acrylate and methylmethacrylate.The product may also be an organic acid, e.g., lactic acid, formic acid,acetic acid, propionic acid, butyric acid, succinic acid, valeric acid,caproic, palmitic acid, stearic acid, oxalic acid, malonic acid,glutaric acid, oleic acid, linoleic acid, glycolic acid,γ-hydroxybutyric acid, a mixture thereof, a salt of any of these acids,or a mixture of any of the acids and their respective salts.

Other intermediates and products, including food and pharmaceuticalproducts, are described in U.S. Ser. No. 12/417,900, the full disclosureof which is hereby incorporated by reference herein.

Materials Paper Feedstocks

Suitable paper feedstocks include paper that is highly pigmented, coatedor filled and can have a low calorific value. Sources of such paperinclude magazines, catalogs, books, manuals, labels, calendars, greetingcards and other high quality printed materials such as prospectuses,brochures and the like. The papers may include at least 0.025% by weightof pigment, filler or coating, e.g., from 0 to 80%, 0 to 50%, 0.1 to50%, 0.1 to 30%, 0.1 to 20%, 0.5 to 2.5%, 0.2 to 15%, 0.3 to 10%, 0.5 to5%.

Other suitable paper feedstocks include high basis weight coated paperand/or paper with a high filler content i.e., at least 10 wt. %. Thesepapers can be printed or unprinted. Examples of this type of feedstockinclude paper having a basis weight, as defined as the weight in pounds(lb) for a ream (500 sheets) of 25″×38″ sheets, of at least 35 lb., forexample at least 45 lb., at least 50 lb., at least 60 lb, at least 70lb. or at least 80 lb. The feedstock includes paper having a basisweight below 330 lb., for example below about 300 lb, below about 250lb, below about 200 lb, below about 150 lb, below about 120 lb, belowabout 110 lb, below about 105 lb or below about 100 lb. For example thebasis weight may be between 35 lb and 330 lb, 35 lb and 120 lb, between35 lb and 110 lb, between 35 lb and 100 lb, between 35 lb and 90 lb,between 45 lb and 120 lb, between 45 lb and 110 lb, between 45 lb and100 lb, between 45 lb and 90 lb, between 50 lb and 120 lb, between 50 lband 110 lb, between 50 lb and 100 lb, between 50 lb and 90 lb, between60 lb and 120 lb, between 60 lb and 110 lb, between 60 lb and 100 lb,between 60 lb and 90 lb, between 60 lb and 120 lb, between 60 lb and 110lb, between 60 lb and 100 lb, between 60 lb and 90 lb, between 70 lb and120 lb, between 70 lb and 110 lb, between 70 lb and 100 lb, between 70lb and 90 lb, between 90 lb and 330 lb, between 90 lb and 300 lb,between 90 lb and 250 lb, between 90 lb and 200 lb, between 90 lb and150 lb, between 90 lb and 110 lb, between 110 lb and 330 lb, between 110lb and 300 lb, between 110 lb and 250 lb, between 110 lb and 200 lb,between 110 lb and 150 lb, between 130 lb and 330 lb, between 130 lb and300 lb, between 130 lb and 250 lb, between 130 lb and 200 lb, or between130 lb and 150 lb, In some embodiments, the papers have relatively highdensity, e.g., greater than 1.11 g/cm³, in some cases from about 1.11 to2 g/cm³ e.g., 1.11 to 1.8 g/cm², 1.11 to 1.6 g/cm², 1.11 to 1.52 g/cm²,1.2 to 1.8 g/cm², 1.2 to 1.6 g/cm², 1.2 to 1.52 g/cm², 1.3 to 1.8 g/cm²,1.3 to 1.6 g/cm² or 1.3 to 1.52 g/cm² Such papers often have a high ashcontent e.g., at least 8 wt. %, at least 10 wt. %, at least 15 wt. %, atleast 20 wt. % or at least 50 wt. %. The ash content can be between 8and 50%, e.g., between 10 and 50%, between 20 and 50%, between 30 and50%, between 10 and 40%, between 20 and 40%, between 10 and 30% orbetween 10 and 20%. The papers can have a high filler content, e.g., atleast 10% by weight, e.g., at least 20 wt %, at least 30 wt %, at least40 wt % or at least 50 wt %. Filler contents can be between 10 and 80%,e.g., between 20 and 80%, between 30 and 80%, between 40 and 80%,between 10 and 70%, between 20 and 70%, between 30 and 70%, between 40and 70%, between 10 and 60%, between 20 and 60%, between 30 and 60% andbetween 40 and 60%. Suitable fillers include clays, oxides (e.g.,titania, silica, alumina), carbonates (e.g., calcium carbonate),silicates (e.g., Talc) and aluminosilicates (e.g., Kaolin). One suitablegrade of coated paper is referred to in the industry as Machine FinishedCoated (MFC) paper. In other embodiments the paper can have a highsurface density (i.e., Grammage), for example, at least 50 g/m², atleast 60 g/m², at least 70 g/m², at least 80 g/m² or at least 90 g/m².The Grammage can be between 50 g/m² and 200 g/m², between 50 g/m² and175 g/m², between 50 g/m² and 150 g/m², between 50 g/m² and 125 g/m²,between 50 g/m² and 100 g/m², between 60 g/m² and 200 g/m², between 60g/m² and 175 g/m², between 60 g/m² and 150 g/m², between 60 g/m² and 125g/m², between 60 g/m² and 100 g/m², between 70 g/m² and 200 g/m²,between 70 g/m² and 175 g/m², between 70 g/m² and 150 g/m², between 70g/m² and 125 g/m², between 70 g/m² and 100 g/m², between 80 g/m² and 200g/m², between 80 g/m² and 175 g/m², between 80 g/m² and 150 g/m²,between 80 g/m² and 125 g/m², between 80 g/m² and 100 g/m², between 130g/m² and 500 g/m², between 130 g/m² and 450 g/m², between 130 g/m² and350 g/m², between 130 g/m² and 300 g/m², between 130 g/m² and 250 g/m²,between 130 g/m² and 200 g/m², between 130 g/m² and 175 g/m², between130 g/m² and 150 g/m², between 200 g/m² and 500 g/m², between 200 g/m²and 450 g/m², between 200 g/m² and 350 g/m², between 200 g/m² and 300g/m², between 200 g/m² and 250 g/m², between 250 g/m² and 500 g/m²,between 250 g/m² and 450 g/m², between 250 g/m² and 350 g/m², between250 g/m² and 300 g/m², between 200 g/m² and 250 g/m², between 300 g/m²and 500 g/m², between 300 g/m² and 450 g/m², or between 300 g/m² and 350g/m².

Coated papers are well known in the paper art, and are disclosed, forexample, in U.S. Pat. Nos. 6,777,075; 6,783,804, and 7,625,441, the fulldisclosures of which are incorporated herein by reference.

Coated papers suitable as feedstock can include paper coated with aninorganic material, for example the same materials used as fillers canbe used in coatings. Additionally, coated papers can include papercoated with a polymer (poly-coated paper). Such paper can be made, forexample, by extrusion coating, brush coating, curtain coating, bladecoating, air knife coating, cast coating or roller coating paper. Forexample, sources of such poly-coated paper include a variety of foodcontainers, including juice cartons, condiment pouches (e.g., sugar,salt, pepper), plates, pet food bags, cups, bowls, trays and boxes forfrozen foods. The poly-coated paper can, in addition to paper, contain,for example, polymers, (e.g., polyethylene, polypropylene, biodegradablepolymers, silicone), latexes, binders, wax, and, in some cases, one ormore layers of aluminum. The poly coated papers can be multi layeredlaminate, for example, made with one or more, e.g., two, three, four,five or more, layers of polyethylene and paper and one or more, e.g.,two, three or more layers of aluminum.

The paper feedstocks typically have a low gross caloric value e.g.,below 7500 Btu/lb e.g, below 7400 Btu/lb, below 7200 Btu/lb, below 7000Btu/lb, below 6800 Btu/lb, below 6600 Btu/lb, below 6400 Btu/lb, below6200 Btu/lb, below 6000 Btu/lb, below 5800 Btu/lb, below 5600 Btu/lb,below 5400 Btu/lb or below 5200 Btu/lb. The gross calorific value can bebetween about 5200 and 7500 Btu/lb e.g., between 6800 and 7000 Btu/lb,between 6700 and 7100 Btu/lb, between 6400 and 7100 Btu/lb, between 6600and 6800 Btu/lb, between 6100 and 6700 Btu/lb, between 6100 and 6300Btu/lb, between 6000 and 6350 Btu/lb, between 5600 and 6400 Btu/lb orbetween 5200 and 5500 Btu/lb. The gross calorific value can be measureusing a bomb calorimeter e.g., as outlined in ASTM method E711.

The paper feedstock can have a basis weight between 35 lb and 330 lb,e.g. 45 lb and 330 lb, 60 and 330 lb, 80 and 330 lb, 60 and 200 lb, 60and 100 lb; optionally a filler content greater than about 10 wt. %,e.g., between 10 and 80 wt. %, between 20 and 80 wt. %, between 30 and80 wt. %, between 30 and 70 wt. %, between 230 and 60 wt. %; optionallya grammage between 50 and 500 g/m², e.g., 70 and 500 g/m², 90 and 500g/m², 90 and 400 g/m², 90 and 300 g/m², 90 and 200 g/m²; and optionallya calorific value between 7500 and 4000 Btu/lb, e.g., 7000 and 4000Btu/lb, 6500 and 4000 Btu/lb, 5000 and 4000 Btu/lb, 6000 and 4500Btu/lb; optionally an ash content between 8 and 50 wt. %, e.g., 10 and80 wt. %, 10 and 60 wt. %, 10 and 50 wt. %, 20 and 50 wt. %.

Some suitable paper feedstock can include a homogeneous sheet formed byirregularly intertwining cellulose fibers. These can include, forexample, Abrasive Papers, Absorbent Paper, Acid Free Paper, Acid ProofPaper, Account Book Paper, Adhesive Paper, Air Dried Paper, Air FilterPaper, Album Paper, Albumin Paper, Alkaline Paper, Alligator ImitationPaper, Aluminum Foil Laminated paper, Ammunition Paper, AnnouncementCard Paper, Anti Rust Paper, Anti-Tarnish Paper, Antique Paper, ArchivalPaper, Art Paper, Asphalt Laminated Paper, Azurelaid Paper, Back LinerPaper, Bacon Paper, Bagasse Paper, Bakers' Wrap, Balloon Paper, Banknoteor Currency Paper, Barograph Paper, Barrier Paper, Baryta Paper, BeediWrap Paper, Bible Paper, Black Waterproof Paper, Blade Wrapping Paper,Bloodproof Paper or Butcher Paper, Blotting Paper, Blueprint Paper,Board, Bogus Paper, Bond Paper, Book Paper, Boxboard, Braille PrintingPaper, Bread Wrapping Paper, Bristol Board, Business Form Paper, ButterWrapping Paper, Burnt Paper, Cable Paper, Calf Paper, Calico Paper,Candy Twisting Tissue, Canvas Paper, Carbonless Paper, Cardboard,Corrugated Cardboard, Carton board, Cartridge paper, Cast Coated Paper,Catalogue Paper, Chart Paper, Check Paper, Cheese Wrapping Paper,Chipboard, Chromo, Coarse Paper (also Industrial Paper), Coatedfreesheet, Coated Paper, Coated White Top Liner, Cockle Finish Paper,Color-fast papers, Commodity Paper, Colored Kraft, Condenser Tissue,Construction Paper, Containerboard, Copier Paper or Laser Paper,Correspondence Papers, Corrugated Board, Corrugated Medium or FlutingMedia or Media, Cotton Paper or Rag Paper, Cover Paper or Cover Stock,Creamwove Paper, Cut Sheet, Damask Paper, Decalcomania Paper, Diazo BasePaper, Document Paper, Drawing Paper, Duplex Board, Duplex Paper,End-leaf Paper, Envelop Paper, Esparto Paper, Extensible Kraft,Extrusion Coated Board, Fax Base Paper, Flame Resistant, Flocked Paper,Fluorescent Paper, Folding Boxboard, Form Bond, Freesheet, FruitWrapping Paper, Gasket Board, Glassine Paper, Glazed Paper, GranitePaper, Gravure Paper, Gray Board, Greaseproof Paper, Green Paper,Groundwood Papers, Gummed Paper, Gypsum Board, Handmade Paper, HangingPaper, Hard Sized Paper, Heat Seal Paper, Heat Transfer Paper, Hi-Fi(High Finish) Paper, Industrial Papers, Insect Resistant, InsulatingBoard, Ivory Board, Japan Paper, Jute Paper, Kraft Bag Paper, Kraftliner, Kraft Paper, Kraft Waterproof Paper, Kraft Wrapping Paper, LabelPaper, Lace Paper, Laid Paper, Laminated Paper, Laminated Linerboard,Latex Paper, Ledger Paper, Lightproof Paper, Liner, Linerboard, LitmusPaper, On Machine Coated, Magazine Paper, Manila, Map Paper, MarblePaper, Matrix Paper, Matt Finished Paper, Mechanical Paper, MellowPaper, Metalization Base Paper, Machine Finished Paper, Machine glazedPaper, Millboard, Mulberry Paper, Natural Colored Papers or Self ColoredPapers, Newsprint, Oatmeal Paper, Offset Paper, Packaging Paper,Paperboard, Pattern Paper, Permanent Paper, Photographic Paper, PlayingCard Stock, Pleading Paper, Poly Extrusion Paper, Postcard Board,Post-Consumer Waste Paper, Poster Paper, Pre-Consumer Waste Paper,Pressure Sensitive Coated Paper, Publishing Paper, Pulp Board, ReleasePaper, Roofing Paper, Safety Paper, Security paper, Self Adhesive Paper,Self Contained Paper, Silicon Treated Paper, Single Faced CorrugatedBoard, Sized Paper, Stamp Paper, Strawboard, Suede Paper,Supercalendered Paper, Surface-Sized, Super Art Paper, Synthetic FiberPaper, Tag Paper, Testliner, Text Paper, Thermal Paper, TranslucentDrawing Paper, Transparent Paper, Treated Paper, Union Kraft, UnglazedPaper, Un-sized Paper, Vaporproof Paper, Varnish-Label Paper, VegetableParchment, Vellum Paper, Velour Paper, Velvet Finish Paper, VulcanizingPaper, Wadding, Wall Paper, Water-Color Paper, Water Finished Paper,Water Resistant Paper, Waterleaf, Waxed Paper, Wet Strength Paper, WhiteTop Liner, Willesden Paper, Wipes or Wiper, Wove, Wrapper, Writing Paperand Xerographic Paper.

The feedstocks described herein can be used in combination with any ofthe biomass feedstocks described in U.S. application Ser. No.12/417,880, filed Apr. 3, 2009, incorporated by reference herein in itsentirety.

Saccharifying Agents

Suitable enzymes include cellobiases and cellulases capable of degradingbiomass.

Suitable cellobiases include a cellobiase from Aspergillus niger soldunder the tradename NOVOZYME 188™.

Cellulases are capable of degrading biomass, and may be of fungal orbacterial origin. Suitable enzymes include cellulases from the generaBacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium,Chrysosporium and Trichoderma, and include species of Humicola,Coprinus, Thielavia, Fusarium, Myceliophthora, Acremonium,Cephalosporium, Scytalidium, Penicillium or Aspergillus (see, e.g., EP458162), especially those produced by a strain selected from the speciesHumicola insolens (reclassified as Scytalidium thermophilum, see, e.g.,U.S. Pat. No. 4,435,307), Coprinus cinereus, Fusarium oxysporum,Myceliophthora thermophila, Meripilus giganteus, Thielavia terrestris,Acremonium sp., Acremonium persicinum, Acremonium acremonium, Acremoniumbrachypenium, Acremonium dichromosporum, Acremonium obclavatum,Acremonium pinkertoniae, Acremonium roseogriseum, Acremoniumincoloratum, and Acremonium furatum; preferably from the speciesHumicola insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthorathermophila CBS 117.65, Cephalosporium sp. RYM-202, Acremonium sp. CBS478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS 169.65,Acremonium acremonium AHU 9519, Cephalosporium sp. CBS 535.71,Acremonium brachypenium CBS 866.73, Acremonium dichromosporum CBS683.73, Acremonium obclavatum CBS 311.74, Acremonium pinkertoniae CBS157.70, Acremonium roseogriseum CBS 134.56, Acremonium incoloratum CBS146.62, and Acremonium furatum CBS 299.70H. Cellulolytic enzymes mayalso be obtained from Chrysosporium, preferably a strain ofChrysosporium lucknowense. Additionally, Trichoderma (particularlyTrichoderma viride, Trichoderma reesei, and Trichoderma koningii),alkalophilic Bacillus (see, for example, U.S. Pat. No. 3,844,890 and EP458162), and Streptomyces (see, e.g., EP 458162) may be used.

Enzyme complexes may be utilized, such as those available from Genencor®under the tradename ACCELLERASE®, for example, Accellerase® 1500 enzymecomplex. Accellerase 1500 enzyme complex contains multiple enzymeactivities, mainly exoglucanase, endoglucanase (2200-2800 CMC U/g),hemi-cellulase, and beta-glucosidase (525-775 pNPG U/g), and has a pH of4.6 to 5.0. The endoglucanase activity of the enzyme complex isexpressed in carboxymethylcellulose activity units (CMC U), while thebeta-glucosidase activity is reported in pNP-glucoside activity units(pNPG U). In one embodiment, a blend of Accellerase® 1500 enzyme complexand NOVOZYME™ 188 cellobiase is used.

Fermentation Agents

The microorganism(s) used in fermentation can be natural microorganismsand/or engineered microorganisms. For example, the microorganism can bea bacterium, e.g., a cellulolytic bacterium, a fungus, e.g., a yeast, aplant or a protist, e.g., an algae, a protozoa or a fungus-like protist,e.g., a slime mold. When the organisms are compatible, mixtures oforganisms can be utilized.

Suitable fermenting microorganisms have the ability to convertcarbohydrates, such as glucose, fructose, xylose, arabinose, mannose,galactose, oligosaccharides or polysaccharides into fermentationproducts. Fermenting microorganisms include strains of the genusSacchromyces spp. e.g., Sacchromyces cerevisiae (baker's yeast),Saccharomyces distaticus, Saccharomyces uvarum; the genus Kluyveromyces,e.g., species Kluyveromyces marxianus, Kluyveromyces fragilis; the genusCandida, e.g., Candida pseudotropicalis, and Candida brassicae, Pichiastipitis (a relative of Candida shehatae, the genus Clavispora, e.g.,species Clavispora lusitaniae and Clavispora opuntiae, the genusPachysolen, e.g., species Pachysolen tannophilus, the genusBretannomyces, e.g., species Bretannomyces clausenii (Philippidis, G.P., 1996, Cellulose bioconversion technology, in Handbook on Bioethanol:Production and Utilization, Wyman, C. E., ed., Taylor & Francis,Washington, D.C., 179-212). Other suitable microorganisms include, forexample, Zymomonas mobilis, Clostridium thermocellum (Philippidis, 1996,supra), Clostridium saccharobutylacetonicum, Clostridiumsaccharobutylicum, Clostridium Puniceum, Clostridium beijernckii,Clostridium acetobutylicum, Moniliella pollinis, Yarrowia lipolytica,Aureobasidium sp., Trichosporonoides sp., Trigonopsis variabilis,Trichosporon sp., Moniliellaacetoabutans, Typhula variabilis, Candidamagnoliae, Ustilaginomycetes, Pseudozyma tsukubaensis, yeast species ofgenera Zygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fungiof the dematioid genus Torula.

Commercially available yeasts include, for example, Red Star®/LesaffreEthanol Red (available from Red Star/Lesaffre, USA), FALI® (availablefrom Fleischmann's Yeast, a division of Burns Philip Food Inc., USA),SUPERSTART® (available from Alltech, now Lalemand), GERT STRAND®(available from Gert Strand AB, Sweden) and FERMOL® (available from DSMSpecialties).

Nutrient Package Ingredients

As discussed above, it may be preferred to include a nutrient package inthe system during saccharification and/or fermentation. Preferrednutrient packages contain a food-based nutrient source, a nitrogensource, and in some cases other ingredients, e.g., phosphates. Suitablefood-based nutrient sources include grains and vegetables, includingthose discussed above and many others. The food-based nutrient sourcemay include mixtures of two or more grains and/or vegetables. Suchnutrient sources and packages are disclosed in U.S. application Ser. No.13/184,138, incorporated by reference herein in its entirety above.

Enzymes for Releasing Nutrients

When a food-based nutrient source is utilized, it is preferred that thesaccharification and/or fermentation mixture further include an enzymesystem selected to release nutrients, e.g., nitrogen, amino acids, andfats, from the food-based nutrient source. For example, the enzymesystem may include one or more enzymes selected from the groupconsisting of amylases, proteases, and mixtures thereof. Such systemsare disclosed in U.S. application Ser. No. 13/184,138, incorporated byreference herein in its entirety.

Fuel Cells

Where the methods described herein produce a sugar solution orsuspension, this solution or suspension can subsequently be used in afuel cell. For example, fuel cells utilizing sugars derived fromcellulosic or lignocellulosic materials are disclosed in U.S.Provisional Application Ser. No. 61/579,568, filed Dec. 22, 2011, thecomplete disclosure of which is incorporated herein by reference.

Other Embodiments

A number of embodiments of the invention have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the invention.

For example, while it is possible to perform all the processes describedherein at one physical location, in some embodiments, the processes arecompleted at multiple sites, and/or may be performed during transport.

Accordingly, other embodiments are within the scope of the followingclaims.

1. A method of producing a sugar comprising providing a paper with ahigh filler content and combining it with a saccharifying agent.
 2. Themethod of claim 1 wherein the filler content is at least 20 wt. %. 3.The method of claim 1 wherein the paper has an ash content of at least 8wt. %.
 4. The method of claim 1 wherein the paper further comprises aprinting ink.
 5. The method of claim 1 wherein the paper is in the formof magazines.
 6. The method of claim 1 further comprising adding afood-based nutrient source to the mixture.
 7. The method of claim 1further comprising adding a microorganism to the paper and producing aproduct or intermediate.
 8. The method of claim 6 wherein the food-basednutrient source is selected from the group consisting of grains,vegetables, residues of grains, residues of vegetables, and mixturesthereof.
 9. The method of claim 7 wherein the product comprises a fuelselected from the group consisting of hydrogen, alcohols, organic acids,hydrocarbons, and mixtures thereof.
 10. The method of claim 7 whereinthe microorganism comprises a yeast and/or a bacteria.
 11. The method ofclaim 1 further comprising physically treating the paper.
 12. The methodof claim 1 further comprising processing the sugar.
 13. The method ofclaim 12 wherein processing comprises separating xylose and/or glucosefrom the sugar.
 14. The method of claim 1 wherein saccharification isconducted at a pH of about 3.8 to 4.2.
 15. The method of claim 11wherein the physical treatment comprises mechanically treating the paperto reduce the bulk density of the paper and/or increase the BET surfacearea of the paper.
 16. The method of claim 6 wherein the food-basednutrient source is selected from the group consisting of wheat, oats,barley, soybeans, peas, legumes, potatoes, corn, rice bran, corn meal,wheat bran, and mixtures thereof.
 17. A method of producing a sugarcomprising providing a paper having a basis weight of at least 35 lb andcombining it with a saccharifying agent.
 18. The method of claim 17wherein the paper has a basis weight between 35 lb and 330 lb.
 19. Themethod of claim 17 wherein the filler content is greater than or equalto 10 wt. %.
 20. The method of claim 17 wherein the paper has an ashcontent of at least 8 wt. %.
 21. The method of claim 17 wherein thepaper further comprises a printing ink.
 22. The method of claim 17wherein the paper is in the form of magazines.
 23. The method of claim17 further comprising adding a food-based nutrient source to themixture.
 24. The method of claim 17 further comprising adding amicroorganism to the paper and producing a product or intermediate. 25.The method of claim 23 wherein the food-based nutrient source isselected from the group consisting of grains, vegetables, residues ofgrains, residues of vegetables, and mixtures thereof.
 26. The method ofclaim 24 wherein the product comprises a fuel selected from the groupconsisting of hydrogen, alcohols, organic acids, hydrocarbons, andmixtures thereof.
 27. The method of claim 24 wherein the microorganismcomprises a yeast and/or a bacteria.
 28. The method of claim 17 furthercomprising physically treating the paper.
 29. The method of claim 17further comprising processing the sugar.
 30. The method of claim 29wherein processing comprises separating xylose and/or glucose from thesugar.
 31. The method of claim 17 wherein saccharification is conductedat a pH of about 3.8 to 4.2.
 32. The method of claim 28 wherein thephysical treatment comprises mechanically treating the paper to reducethe bulk density of the paper and/or increase the BET surface area ofthe paper.
 33. The method of claim 23 wherein the food-based nutrientsource is selected from the group consisting of wheat, oats, barley,soybeans, peas, legumes, potatoes, corn, rice bran, corn meal, wheatbran, and mixtures thereof.